Color fixing agents



United States PatentG 0LOR FIXING AGENTS Alexander F. Gortvai, Utica, N.Y., assignor to United Merchants and Manufacturers, Inc., New York, N.Y., a corporation of Delaware No Drawing. Filed Nov. 19, 1956, Ser. No. 622,790

11 Claims. (Cl. 8-74) This invention relates to improvements in the coloring of textiles, or more particularly to the production of a series of new chemical compounds and their use in insolubilizing dyestuffs on fabrics.

It is an object of the invention to improve the fastuess to laundering of dyeings on textile fabrics. Another object is the insolubilization of water soluble dyestufis on cellulosic textiles. Still another object is the production of new chemical compounds. A further object is the after-treatment of dyed fabrics with new compounds for the improvement of fastness characteristics.

A still further object is the production of new chemical compounds adapted to decrease the shrinkage on Washing and to improve the washfastness of dyed cellulosic textiles. Another object is a process whereby dyeings on cellulosic textiles may be rendered fast to washing, and the dyed textiles may be rendered resistant to creasing in a single operation. Still another object is the improvement of washfastness of dyed textiles and the control of shrinkage of said textiles on washing in a single operation. Other objects will appear hereinafter.

The dyestuffs falling into the class known as direct dyes or substantive dyes for cellulosic fabrics possess numerous advantages which result in their use in extensive quantities despite their poor fastness properties. Because of the general atractiveness of the colors obtainable with such dyestufis, as well as their relatively low cost and simplicity of application, such dyestuffs are widely used despite their tendency to be leached out or to bleed when laundered.

According to some theorists, direct dyestufis are adsorbed by cellulosic fabrics and asa result they coat the walls of the micellular passages within the fibers. The concave form of such walls is said to increase the effect of the attractive forces involved. However, since such dyes are water soluble, no matter how many times the goods are washed, each successive washing will remove some dyestuff from the fiber.

Many treatments have been proposed to improve the fastness of such dyeings, some with little effect,-0thers with somewhat better effect. According to the present invention, it is possible to. manufacture new chemical substances, which, when applied to fabrics according to the process of this invention, will so improve the fastness properties of dyeings made with substantive dyestuffs, that the said properties compare favorably with those of dyes ings made with vat dyestuffs.

The usefulness of the materials of theinvention is not limited to dyeings made with substantive dyestuffs, marked improvement of washfastness comparable in degree to that observed with substantive dyestuffs having been observed when the materials of the invention were applied to fabrics previously dyed with basic, acid and chrome dyestuffs. In addition, when these substances are applied to dyed materials which when untreated showed an appreciable or undesirable shrinkage on washing, the shrinkage on washing'is markedly reduced.

In practising the invention, an organic nitrogen com-- 2,973,239 Patented Feb. 28, 1961 pound having two or more reactive nitrogen groups, such as dicyandiamide, is reacted with an aldehyde, for ex ample formaldehyde, in aqueous alkaline solution. The pH of the solution may then be adjusted almost to the neutral zone, but preferably slightly on thebasic side thereof in the range from pH 7.5-8.2, and the precondensate produced by the first reaction may then be reacted with a neutral ester of an inorganic acid, for example, diethyl sulfate or other quaternizing agent, to form a new type of compound. The reaction is a typical quaterniza tion and takes place only on the quaternary nitrogen atoms, and the result is a water soluble and non-solvent soluble strongly cationic compound. Thus the applicants reaction may be represented as follows: (See Anthony U. Schwartz and James W. Perry Surface Active Agents, 1949, page 169.)

This formulation represents a cationic quaternized compound: specifically, a quaternary ethyl sulphate.

The precondensate, which is the basic compound for quaternization, is ionized only in a limited way, and it is anionic in nature. The quaternized compound is highly cationic, which is expressed in a high degree of incompatibility-with any anionic compounds (anions). For example, a dilutedwater solution of thecolor-fixing agent mixed with a diluted. Glauber salt, sodium hydroxide, ammonium hydroxide, or even common salt solution gives a heavy precipitate. The precondensate, before quaternization, does not show this highly characteristic ionic behavior within a non-basic pH range.

After the reaction of the precondensate with the quaternizing agent is complete, the quaternization product, a viscous oily liquid, may be dried under high vacuum, to a powder. In this form the material may be stored indefinitely. Alternatively, the liquid may be stored for use and then diluted as desired for application to fabrics. In this case, however, some care is necessary to see that the material is not overheated, as the viscosity tends to increase in storage, a process which is accelerated by elevated temperatures. Notwithstanding this tendency, samples have been stored for as much as six months at room temperature without deleterious results.

It has been found that the color fixing agents or compounds produced inthe manner just outlined prevent bleeding of the color by forming water-insoluble precipitates with any dyestufl? compound containing an (OH) Cl, (SO or (SO OH)-" radical under the usual conditions of temperature and pH encountered in the customary finishing treatments for textiles. The compounds also give precipitates with the above ions in almost any circumstances, except in the presence of strong acids, where the pH is much lower than 3. When such compounds are applied in the manner hereinafter described to fabrics. dyed, for example, with so-called direct dyes, the fastness of the dyeings to washing is greatly improved. Instead of the. usual, poor fastnesses characteristic of such dyeings, fastnesses comparable with those of vat dyeings are the result. Nor are these the only improvements noted; in most cases a very high degree of shrinkage control is also produced.

In practice the ratio of moles of amide to moles of formaldehyde may range from 1:1 to 1:5, but a ratio of 1:2 has been found most satisfactory from the standpoint of results obtained. The preferred proportion for diethyl sulfate is approximately mole for each mole of amide, but the amount used may range from about V2 mole to V2 mole per mole of amide.

If desired, an aliphatic alcohol having less than eight carbon atoms may be incorporated into the precondensate with satisfactory results. For example, up to 1% moles of methanol for each mole of dicyandiamide may be employed in the original reaction mixture, while using the same amounts of the other ingredients. Such products have somewhat improved stability to storage as compared with products of the invention prepared without using added alcohols. Besides methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, butyl alcohol, etc. may be employed.

As will be apparent, other nitrogen compounds may replace dicyandiamide. Of these, guanidine, guanylurea, biguanide and melamine may be mentioned. In like manner other aldehydes may be used to replace formal dehyde. For example, glyoxal, acetaldehyde, or benzaldehyde give satisfactory results. And in addition, other neutral esters may replace diethyl sulfate. As examples, dimethyl sulfate and benzyl chloride may be mentioned.

In employing the products of the invention for the fixing of dyestuffs on fabrics, the fabrics may first be dyed with a solution of a water soluble dyestuif, such as, for example, a 5% solution of Pontamine Fast Blue SFL. The fabric may then be dried in the usual manner, and subsequently impregnated with a solution containing one of the compounds of the invention. After impregnation, the fabric may be dried and cured, or rinsed and dried, as desired.

The manner of application of the solution to the fabric is not critical and may be any conventional method such as immersion in a dye-jig or beck, or a dip and nip, or a nip only on a padder. Alternatively, the fabric may be immersed in the solution in any suitable vessel for a period of from to 40 minutes.

In Whatever manner the solution is applied to the goods, a pick-up of 75%-80% on the weight of the goods is preferred, although these figures may be varied within reasonable limits, as will be apparent. The amount of colorfixing compound used may vary from about 1 to about 60 percent by weight. However, a concentration in the range of from about 1 to about 8 percent by weight is generally preferred. Of these latter, concentrations ranging from about 1% to about 4% may be used with light shades, and concentrations ranging from about 6% to about 8% may be used with darker shades.

The materials of the invention may be applied alone, or in combination with synthetic resins. or other treating agents. Thus, the treating solution may include a product of the invention, together with a melamine formaldehyde condensation product, or a urea formaldehyde precondensate. In such cases, the conventional catalysts for these materials, e.g. boric acid, lactic acid, tartaric acid, ammonium salts, etc., may be incorporated into the treating bath. It has also been found beneficial to incorporate small amounts of certain metal salts, e.g. copper chloride or aluminum chloride into the treating bath. When such salts are employed, no other catalyst for the synthetic resins is needed. The presence of other ingredients would not, however, afliect the amount of the colorfixing compound used.

The following examples are included to illustrate the preparation of the compounds of the invention, and the use thereof in the fixing of dyes on fabrics.

Example I 400 parts or 4.76 moles by weight of dicyandiamide were added to 800 parts or 9.87 moles by weight of an aqueous solution of formaldehyde containing 37% by weight of formaldehyde. 18 parts or Mr mole by weight of a 25% aqueous solution of ammonium hydroxide were then added. The temperature of the mixture was raised by heating to 60-75 C. and maintained at this level until the primary condensation reaction was complete, as evidenced by the clarification ofthe solution The pH of the solution was then adjusted to 7.2 by the addition of a small amount of diethyl sulfate, and then 160 grams or 1.04 moles of diethyl sulfate were added. As the reaction proceeded the temperature of the mixture was allowed to reach 85-95 C., after which cooling was applied to control the reaction and keep the temperature within these llIIlitS. When all of the diethyl sulfate was consumed the evolution of gas ceased and the reaction was complete. The reaction yielded 113 grams of a heavy viscous liquid. It was suitable for application to fabrics, or might be stored for periods from two weeks to a year or more provided overheating was avoided.

If desired, the water present in the liquid product might be removed by evaporation under high vacuum. Drying produced a dry powder of superior stability.

Example II The procedure of Example I was repeated using the following quantities:

Example III The procedure of Example I was repeated using the following quantities:

400 parts or 4.76 moles by weight dicyandiamide 800 parts or 9.87 moles by weight 37% formaldehyde solution 18 parts or 0.25 mole by weight 25% ammonium hydroxide solution 110 parts or 0.72 mole by weight diethylsulfate Example I V The procedure of Example I was repeated using the following quantities:

400 parts or 4.76 moles by weight dicyandiamide 800 parts or 9.87 moles by weight 37% formaldehyde solution 18 parts or 0.25 mole by weight 25% ammonium hydroxide solution 200 parts or 1.50 moles by weight diethylsulfate Example V The procedure of Example I was repeated using the following quantities:

400 parts or 4.76 moles by weight dicyandiamide 800 parts or 9.87 moles by weight 37% formaldehyde solution 18 parts or 0.25 mole by weight 25% ammonium hydroxide solution 360 parts or 2.25 moles by weight diethylsulfate Example VI The procedure of Example I was repeated using the following quantities:

400 gr. or 4.76 moles dicyandiamide 800 gr. or 9.87 moles 37% formaldehyde solution 18 gr. or 0.25 11101 25 ammonium hydroxide solution gr. or 1.10 moles dimethylsulfate Example VII The procedure of Example I was repeated using the following quantities:

Example VIII The procedure of Example I was repeated using the following quantities:

40 parts or 0.476 mole by weight dicyandiamide 40 parts or 0.493 mole by weight 37% formaldehyde solution 2 parts or 0.025 mole by weight 25% ammonium hydroxide solution 16 parts or 0.10 mole by weight diethyl sulfate Example IX The procedure of Example I was repeated using the following quantities:

40 parts or 0.476 mole by weight dicyandiamide 200 parts or 2.467 moles by weight 37% formaldehyde solution 2 /2 parts or 0.036 mole by weight 25 ammonium hydroxide solution 16 parts or 0.10 mole by weight diethyl sulfate Example X 40 parts or 0.476 mole by weight of dicyandiamide, 80 parts or 0.98 mole by weight of a water solution containing 37% by weight of formaldehyde, and 6 parts or 0.19 mole by weight of methanol were charged into a reaction vessel. 2 parts or 0.025 mole by weight of a 25% ammonium hydroxide solution were then added. The reaction mixture was then heated to 60-75 C. and held at this temperature until the primary condensation reaction was complete, as indicated by the clarity and homogeneity of the solution. The pH of the mixture was then adjusted to 7.2 by the addition of a small amount of diethyl sulfate. An additional 16 parts by weight of diethyl sulfate were then added and the temperature of the mixture was allowed to rise to 8595 C., after which cooling was applied to maintain the temperature within this range. When all of the diethyl sulfate was consumed, the evolution of gas ceased, and the reaction was complete. The product which had a moisture content of approximately 31%, could be used or stored as is, or it might be dried by means of vacuum evaporation.

Example XI The procedure of Example X was repeated using the following proportions:

40 parts or 0.476 mole by weight dicyandiamide 80 parts or 0.98 mole by weight 37 formaldehyde solution 20 parts or 0.625 mole by weight methanol 2 parts or 0.025 mole by weight 25% ammonium hydroxide solution 16 parts or 1.10 mole by weight diethyl sulfate Example XII The procedure of Example X was repeated using the following materials and proportions:

40 parts or 0.476 mole by weight dicyandiamide 150 parts or 0.77 mole by weight 30% aqueous solution of glyoxal 6 parts or 0.075 mole by weight 25% ammonium hydroxide solution 16 parts or 0.10 mole by weight diethyl sulfate Example XIII The procedure of Example X was repeated using the following materials and proportions:

40 parts or 0.476 mole by weight dicyandiamide 120 parts or 0.91 mole by weight 33% aqueous acetaldehyde solution 2 parts or 0.025 mole by Weight 25% ammonium hydroxide solution 16 parts or 0.10 mole by weight diethyl sulfate A melamine formaldehyde condensation product was produced in the customary manner using 40 parts by weight of melamine, parts by weight of 37% formaldehyde solution, and 2 parts by weight of ammonium hydroxide solution. 16 parts by weight of diethyl sulfate were then dispersed in three times the amount of water at 40 C. with the aid of approximately 3 parts by weight of a dispersing agent such as that sold under the trade name Igepal CA by the General Dyestufl Corporation. The resulting dispersion was added to the condensation product just prepared, and the reaction was allowed to proceed to completion at a temperature in the range of -95 C.

The product was stored at a temperature not exceeding 23 C. for future use on fabrics as described hereinafter.

Example XV The following ingredients were charged into a reaction vessel:

50 parts by weight biguanide 80 parts by weight 37% formaldehyde solution 2 parts by weight 25 ammonium hydroxide solution The temperature was raised to 75 C. and held at this level until the primary condensation reaction was complete as indicated by the formation of a clear solution. The pH was then adjusted to 7.2 by the addition of a small amount of diethyl sulfate. 16 parts by weight of diethyl sulfatewere then added and the reaction was allowed to proceed to completion (as evidenced by the cessation of evolution of gas) at a temperature of 8595 C. The product was stored at a temperature less than 23 C. for future use on textiles.

Example XVI Samples of an all spun rayon gabardine of a Weight of approximately 200 grams to the yard were dyed with each of the following in the customary manner:

(1) 4% Sunfast Blue 4 GLR (B & H Chemical Co.) (2) 5% Pontamine Fast Blue SFL (Du Pont) (3) 6% Indigene Black BG conc. (Ciba) The fabric dyed in each dyeing was separated into two portions, one of which was set aside for testing, and the other was given further treatment as described here inafter.

Example XVII An impregnating liquor having the following composition was then prepared:

Parts by weight Liquid product of Example I 6 Water 94 The portions of dyeings 1, 2 and 3 of the previous example which had been set aside for further treatment were then separately immersed in portions of the above impregnating liquor in a dye beck for 40 minutes and then squeezed and dried without rinsing. After drying, the samples were cured at C. for five minutes.

Samples of dyeings 1, 2 and 3 of Example XVI, and of the same dyeings after-treated according to the present example, were then tested according to AATCC standard test method 36-45 for colorfastness to commercial and domestic washing. Colorfastness of the untreated samples were found to be class I or poor; i.e., as a result of the test there was appreciable staining of the test cloth attached to the dyed fabric. colorfastness of the treated samples, on the other hand, was class IV or very good; i.e., no appreciable change in color, and no appreciable staining of attached cloth in test No. 3 (160 F. or 71 C.).

Ft Example XVIII A treating liquor of the following proportions was prepared:

Parts by weight Urea-formaldehyde precondensate 20 Melamine-formaldehyde precondensate 2 Liquid product of Example I 6 Aqueous lactic acid solution (60%) 1 Water 71 Samples of the untreated material dyed according to dyeings Nos. 1, 2, and 3 of Example XVI were impregnated with the above treating liquor on a three bowl pad, employing a dip and nip with pressure adjusted for 70% pick-up. After impregnation and drying, the samples were cured for five minutes at 160 C. When tested according to AATCC test standard method 36-45, these samples showed very' good colorfastness, i.e. class IV, according to AATCC standards.

Example XIX A treating liquor of the following proportions was prepared:

Parts by weight Urea-formaldehyde precondensate 20 Melamine formaldehyde precondensate 2 Liquid product of Example I 8 60% aqueous lactic acid solution 1 Water 69 Samples of the untreated material dyed according to dyeings Nos. 1, 2, and 3 of Example XVI were impregnated with the above treating liquor on a three bowl pad, employing a dip and nip with pressure adjusted for 70% pick-up. After impregnation and drying, the samples were cured for five minutes at 160 C. When tested according to AATCC test standard method 3645, these samples showed very good. colorfastness, i.e. class IV, according to AATCC standards.

Example XX A treating liquor of the following proportions was prepared:

Parts by weight Urea-formaldehyde resin 20 Liquid product of Example I 8 60% aqueous lactic acid solution 1 Water 71 Samples of the untreated material dyed according to dyeings Nos. 1, 2 and 3 of Example XVI were impregnated with the above treating liquor on a three bowl pad, employing a dip and nip with pressure adjusted for 70% pick-up. After impregnation and drying, the samples were cured for five minutes at 160 C. When tested according to AATCC test standard method 36-45, these samples showed very good colorfastness, i.e. class IV, according to AATCC standards.

Example XXI A treating liquor of the following proportions was prepared:

Parts by weight Urea-formaldehyde resin 20 Liquid product of Example I 60 60% aqueous lactic acid solution 1 Water 19 Samples of the untreated material dyed according to dyeings Nos. 1, 2 and 3 of Example XVI were impregnated with the above treating liquor on a three bowl pad, employing a dip and nip with pressure adjusted for 70% pickup. After impregnation and drying, the samples were cured for five minutes at 160 C. When tested according to AATCC test standard method 36-45, these samples showed very good colorfastness, i.e. class IV, according to AATCC standards.

Example XXII Further samples of an all spun rayon gabardine of a weight of approximately 200 grams to the yard were dyed with-each of the following in the. customary manner: V

(4 8% Coprantine Green G (Ciba) (5) 4% Niagara Sky Blue 6B (National Aniline) (6) 3% Cuprofix Rubinol BL Sandoz) Portions of each of these dyeings were set aside for testing and the remainder were used for further treatment.

Example XXIII A treating batch of the following composition was then prepared:

Parts by weight Liquid product of Example I 6 Copper chloride 0.8 Water 93.2

Samples of each of dyeings Nos. 4, 5 and 6 were sepa rately immersed in portions of the above bath for approximately 40 minutes at a temperature of about 71 C., after which they were rinsed and dried.

Samples of dyeings Nos. 4, 5 and 6 before and after treatment were then tested according to AATCC test method 36-45. Those samples after-treated in the treating bath showed class IV, or very good colorfastness, Whereas the dyed but untreated samples showed class I, or poor colorfastness.

Example XXIV A solution of the following proportions was prepared:

300 parts by weight of urea-formaldehyde precondensate,

e.g. Rhonite 610 of Rohm and Haas Company 60 parts by weight of the liquid product of Example I 8 parts by weight of copper chloride 632 parts by weight of water Example XXV 'A treating solution of the following components was prepared:

200 parts by weight urea-formaldehyde resin 20 parts by weight melamine-formaldehyde resin 60 parts by weight liquid product of Example I 8 parts by weight copper chloride 712 parts by weight water Samples of dyeings Nos. 4, 5 and 6 of Example XXII were given a dip and nip on a three bowl pad employing the above solution. The treated samples were then dried', after which they were cured five minutes at C. Colorfastness, determined by AATCC test method 36- 45, was very good.

Example XXVI Eurther samples of an all spun rayon gabardine of a weight of approximately 200 grams to the yard were dyed with each of the following in the customary manner:

(7) 0.5% Sunfast Blue 4 GLR (8) 1% Pontamine Fast Blue SFL (9) 1% Indigene Black BG concentrate Portions of each of these dyeings were set aside for testing, and the remainder were used for further treatment.

Exampie XX VII A treating liquor of the following composition was prepared:

Parts by weight Samples of the untreated material dyed according to dyeings Nos. 7, 8 and 9 of Example XXVI were impregnated with the above treating liquor on a three bowl pad, employing a dip and nip with pressure adjusted for 70% pick-up. After impregnation and drying, the samples were cured for five minutes at 160 C. When tested according to AATCC test standard method 36-45, these samples showed very good colorfastness, i.e. class IV, according to AATCC standards, whereas the dyed but untreated samples showed class I, or poor colorfastness.

This application is a continuation-in-part of co-pending application Serial Number 300,130, filed July 21, 1952.

What is claimed is:

1. A process for the production of water soluble condensation products which includes the steps of reacting about 1 mole of dicyandiamide and from about 1 mole to about moles of formaldehyde in alkaline aqueous solution by heating said solution to a temperature of from 60 C. to 75 C. and maintaining the temperature at that level until the reaction is complete, adjusting the pH of the solution to 7.2, and thereafter reacting the precondensate so formed with from about ,4 mole to about /2 mole of diethyl sulfate by adding the diethyl sulfate to the precondensate and allowing the temperature of the mixture thus formed to reach a level of from 85 C. to 95 C. and keeping the temperature within these limits until the second reaction is complete as evidenced by cessation of gas evolution.

2. A process for the production of water soluble condensation products including the steps of reacting about 1 mole of an organic nitrogen compound selected from the group consisting of dicyandiamide, guanidine, and guanyl urea with from about 1 mole to about 5 moles of an aldehyde selected from the group consisting of formaldehyde, acetaldehyde, benzaldehyde, and glyoxal in alkaline solution by heating such solution to a temperature of 60 C. to 75 C. and maintaining the temperature at that level until the reaction is complete, adjusting the pH of the solution to 7.2, and subsequently reacting the precondensate thus formed with from about mole to about /2 mole of diethyl sulfate by adding the diethyl sulfate to the precondensate and allowing the temperature of the mixture so formed to reach from 85 C. to 95 C. and keeping the temperature within these limits until the second reaction is complete, as evidenced by cessation of gas evolution.

3. A water soluble product of the process of claim 2.

4. Process for the preparation of water soluble condensation products including the steps of reacting about 1 mole of dicyandiamide with about 2 moles of formaldehyde in an alkaline aqueous solution by heating said solution to a temperature of from about 60 C. to about 75 C. and maintaining the temperature at that level until the reaction is complete, adjusting the pH of the solution to 7.2, and then reacting the precondensate formed by the first reaction with about /5 mole of diethyl sulfate by adding the diethyl sulfate to the precondensate and allowing the temperature of the mixture thus formed to reach a level from 85 C. to 95 C. and keeping the temperature within these limits until the second reaction is complete, as evidenced by cessation of gas evolution.

5. Process for the preparation of water soluble dyefixing agents which includes the steps of reacting about 1 mole of dicyandiamide with from about 1 mole to about 5 moles of formaldehyde in aqueous alkaline solution by heating said solution to a temperature of from 60 C. to 75 C. and maintaining the temperature at that level until the reaction is complete, adjusting the pH of the solution to 7.2, and subsequently reacting the precondensate formed by the first reaction with about /5 mole of diethyl sulfate by adding the diethyl sulfate to the precondensate and allowing the temperature of the mixture thus formed to reach a level of from C. to C. and keeping the temperature within these limits until the second reaction is complete as evidenced by cessation of gas evolution.

6. Preparation of water soluble color fixing compounds which includes the steps of reacting 1 mole of dicyandiamide with 2 moles of formaldehyde in aqueous alkaline solution by heating said solution to a temperature of from 60 C. to 75 C. and maintaining the temperature at that level until the reaction is complete, adjusting the pH of the solution to 7.2, and then reacting the precondensate so formed with about /5 mole of diethyl sulfate by adding the diethyl sulfate to the precondensate and allowing the temperature of the mixture thus formed to reach a level of from 85 C. to 95 C. and keeping the temperature within these limits until the reaction is completed as evidenced by cessation of gas evolution.

7. A process for the preparation of water soluble color fixing agents which includes the steps of reacting about 1 mole of dicyandiamide dissolved in from up to1% moles of methyl alcohol with from about 1 mole to about 5 moles of formaldehyde in aqueous alkaline solution by heating said solution to a temperature of from 60 C. to 75 C. and maintaining the temperature at that level until the reaction is completed, adjusting the pH of said solution to 7.2, and subsequently reacting the precondensate thus formed with from about 1/20 mole to about /2 mole of diethyl sulfate by adding the diethyl sulfate to the precondensate and allowing the temperature of the mixture thus formed to reach a level of from 85 C. to 95 C. and keeping the temperature within these limits until the second reaction has been completed as evidenced by cessation of gas evolution.

8. Process for the preparation of water soluble dyefixing agents including the steps of reacting about 1 mole of an organic nitrogen compound selected from the group of nitrogen containing compounds which consists of dicyandiamide, guanidine, and guanyl urea, and an aliphatic alcohol having less than eight carbon atoms, with from about 1 mole to about 5 moles of an aldehyde selected from the group of aldehydes consisting of formaldehyde, glyoxal, acetaldehyde and benzaldehyde in alkaline solution by heating said solution to a temperature of from 60 C. to 75 C. and maintaining the temperature at that level until the reaction is complete, neutralizing said solution, and subsequently reacting the precondensate formed in the first reaction with from about 1/ 20 mole to about /2 mole of diethyl sulfate by adding the diethyl sulfate to the precondensate and allowing the temperature of the mixture thus formed to reach a level of from 85 C. to 95 C. and keeping the temperature within these limits until the second reaction is complete as evidenced by cessation of gas evolution.

9. Process for the production of water soluble condensation products which includes the steps of reacting about 1 mole of dicyandiamide and about 2 moles of formaldehyde in alkaline aqueous solution by heating said solution to a temperature of from 60 C. to 75 C. and maintaining the temperature at that level until the reaction is complete, adjusting the pH of the solution to 7.2, and subsequently reacting the precondensate so formed with from about 1/ 20 mole to about /2 mole of an ester of an inorganic acid selected from the group of inorganic acids consisting of diethyl sulfate, dimethyl sulfate, and

benzylchloride, by adding the ester to the precondensate and allowing the temperature of the mixture thus formed to reach a level of from 85 C. to 95 Y C. and keeping the temperature within these limits until the second reaction is complete as evidenced by cessation of gas evolution.

10. Process for the preparation of water soluble dyefixing agents including the steps of reacting about 1 mole of dicyandiam-ide with from about 1 mole to about 5 moles of formaldehyde in aqueous alkaline solution by heating said solution to a temperature of from C. to C. and maintaining the temperature at that level until the reaction is complete, adjusting the pH of the solution to 7.2, and then reacting the precondensate so formed with an amount ranging from about 1/20 mole to about V2 mole of diethyl sulfate by adding the diethyl sulfate to the precondens-ate and allowing the temperature of the mixture thus formed to reach a level of from C. to C. and keeping the temperature within these limits until the second reaction is complete as evidenced 'by cessation of gas evolution. a

11. Process of treating textile fabrics including thesteps of dyeing with a water soluble dyestufi, thereafter treating the dyed fabric with an aqueous treating solution comprising from about 2 to about 8 percent by weight of the water soluble product of the process of claim 1, about 20 percent by weight of a urea formaldehyde precondensate, about 0.8 percent by weight of copper chloride, and the balance water, and thereafter drying and curing the treated fabric.

References Cited in the file of this patent UNITED STATES PATENTS 2,526,106 Albrecht et al Oct. 17, 1950 2,567,238 Sellet Sept. 11, 1951 2,768,055 Streck et a1. Oct. 23, 1956 

1. A PROCESS FOR THE PRODUCTION OF WATER SOLUBLE CONDENSATION PRODUCTS WHICH INCLUDES THE STEPS OF REACTING ABOUT 1 MOLE OF DICYANDIAMIDE AND FROM ABOUT 1 MOLE TO ABOUT 5 MOLES OF FORMALDEHYDE IN ALKALINE AQUEOUS SOLUTION BY HEATING SAID SOLUTION TO A TEMPERATURE OF FROM 60*C. TO 75*C. AND MAINTAINING THE TEMPERATURE AT THAT LEVEL UNTIL THE REACTION IS COMPLETE, ADJUSTING THE PH OF THE SOLUTION TO 7.2, AND THEREAFTER REACTING THE PRECONDENSATE SO FORMED WITH FROM ABOUT 1/20 MOLE TO ABOUT 1/2 MOLE OF DIETHYL SULFATE BY ADDING THE DIETHYL SULFATE TO THE PRECONDENSATE AND ALLOWING THE TEMPERATURE OF THE MIXTURE THUS FORMED TO REACH A LEVEL OF FROM 85* C. TO 95*C. AND KEEPING THE TEMPERATURE WITHIN THESE LIMITS UNTIL THE SECOND REACTION IS COMPLETE AS EVIDENCED BY CESSATION OF GAS EVOLUTION. 